Bisthiol-Assisted Multilayers' Self-Assembly of Gold Nanoparticles: Synthesis,Characterization, Size Control and Electrocatalytic Applications

The layer-by-layer (LBL) approach has been utilized to self-assemble multilayers films of citrate-stabilized gold nanoparticles (AuNPs) on polycrystalline gold (poly-Au) substrates. 1,4-benzenedimethanethiol (BDMT) was used as a cross linker to bind every two successive AuNPs layers. The transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) techniques were employed to confirm the existence of the alternative layers of AuNPs and BDMT in the self-assembled multilayers film. The AuNPs modified poly-Au electrode showed a significant electrocatalysis towards the reduction of oxygen (a positive potential shift of about 100 mV was observed in the reduction peak potential compared to that obtained at the bare poly-Au electrode). The AuNPs tend to aggregate during their assembling to different extent which markedly depends on the substrate geometry and roughness. An effort was dedicated to understand and control the aggregation phenomenon.     

Synthesis and Self-Aggregation of Chlorophyll-a Derivatives Possessing a Hydroxymethyl Group in the C20-Substituent with Ethynylene and/or Phenylene Linkers

Chlorophyll(Chl)-a derivatives containing some rigid linkers in the C20 substituents, which were inserted between a hydroxymethyl group and the chlorin π-skeleton, were synthesized and their self-aggregation abilities were investigated. Measurements of electronic absorption, circular dichroism and infrared absorption spectra revealed that the zinc complex of a Chl-a derivative bearing a (p-ethynyl)benzyl alcoholic moiety at the C20-position gave its J-aggregates in an aqueous micellar solution through the hydrogen and coordination bonding. These results exhibited the potential of Chl-a derivatives bearing a hydroxyl group in the C20 substituents as the model compounds for chlorosomal light-harvesting antennas.     

Functional polymers based on high hydrophilicity of poly(2-methyl-2-oxazoline)

Polymers of the family of 2-substituted 2-oxazolines have the general structure of poly(N-acylethylenimine), whose hydrophilic/lipophilic properties vary according to the substituent, i.e., the acyl group of the polymer. Of special interest is the polymer of 2-methyl-substituted monomer, which has a strong affinity for water. Another useful feature of the 2-oxazoline family is the fact that its polymerization reaction is quite clean without disturbance by chain transfer and termination. On the basis of the above characteristics, three kinds of novel materials of functional polymers have been explored:

• 1. Non-ionic polymeric surfactants.
• 2. Non-ionic hydrogels.
• 3. Block copolymer with silica gel: Organic/inorganic polymers hybrids.

     

Polymerization chemistry of the family of cyclic imino ethers

Characteristics of the polymerization mechanisms of the family of cyclic imino ethers are described. The variety of the mechanism of propagation has been systematized on the basis of the nature of propagating species, i.e., cationic or electrophilic covalent (dipole) species. In the polymerizations of 2-alkyl cyclic imino ethers (5- and 6-membered), propagation mechanism via one of these two different species has been established, which is dependent upon the relative nucleophilic reactivities of the monomer and the counter anion derived from initiator. The polymerization of cyclic pseudoureas having a cyclic amine substituent at 2-position proceeds in two different ways. Ionic propagation leads to the single isomerization/ring-opening polymerization involving only the cyclic imino ether ring. On the other hand, covalent propagation gives rise to the double isomerization ring-opening polymerization involving the two rings of cyclic imino ether and cyclic amine. Polymerization of 5-membered cyclic iminocarbonate with a sulfonate initiator proceeds through the isomerization/ring-opening of 2-oxazoline ring. The same monomer was isomerized to the corresponding cyclic urethane when it was treated with benzyl bromide.